Derivatives of polyamines with one primary amine and secondary of tertiary amines

ABSTRACT

A dispersant derivatized from a functionalized hydrocarbon and a polyamine having one primary amine and 1-10, preferably 3-8 secondary or tertiary amines; preferably where said functionalized hydrocarbon is a Koch-derived hydrocarbon.

CROSS REFERENCE

This application is a continuation-in-part of U.S. Ser. No. 992,403,filed Dec. 17, 1992, now abandoned in favor of continuing applicationU.S. Ser. No. 08/534,891, filed Sep. 25, 1995.

BACKGROUND OF THE INVENTION

The present invention is directed to dispersant prepared from polymersfunctionalized by a Koch reaction and polyamines containing one primarynitrogen group and at least one secondary or tertiary nitrogen. Inparticular, the invention is directed to Koch functionalized polymers,especially poly alpha-olefins or polyethylene/alpha-olefins derivatizedwith so-called one-armed amines containing one (preferably only one)primary amine group and one or more secondary or tertiary amine groups.

The present invention is directed to an improved polymer functionalizedby the Koch reaction more particularly by reacting at least onecarbon-carbon double bond with carbon monoxide in the presence of anacidic catalyst and a nucleophilic trapping agent to form a carbonyl orthiocarbonyl functional group, and derivatives thereof.

The term "polymer" is used herein to refer to materials comprising largemolecules built up by the repetition of small, simple chemical units. Ina hydrocarbon polymer those units are predominantly formed of hydrogenand carbon. Polymers are defined by average properties, and in thecontext of the invention polymers have a number average molecular weight(Mn) of at least 500. The term "hydrocarbon" is used above herein torefer to non polymeric compounds comprising hydrogen and carbon havinguniform properties such as molecular weight. However, the term"hydrocarbon" is not intended to exclude mixtures of such compoundswhich individually are characterized by such uniform properties. Bothhydrocarbon compounds as well as polymeric compounds have been reactedto form carboxyl group-containing compounds and their derivatives.Carboxyl groups have the general formula --CO--OR, where R can be H, ahydrocarbyl group, or a substituted hydrocarbyl group.

The synthesis of carboxyl group-containing compounds from olefinichydrocarbon compounds, carbon monoxide, and water in the presence ofmetal carboxyls is disclosed in references such as N. Bahrmann, Chapter5, Koch Reactions, "New Synthesis with Carbon Monoxide" J. Falbe;Springer-Verlag, New York, 1980. Hydrocarbons having olefinic doublebonds react in two steps to form carboxylic acid-containing compounds.In the first step an olefin compound reacts with an acid catalyst andcarbon monoxide in the absence of water. This is followed by a secondstep in which the intermediate formed during the first step undergoeshydrolysis or alcoholysis to form a carboxylic acid or ester. Anadvantage of the Koch reaction is that it can occur at moderatetemperatures of -20° C. to +80° C., and pressures up to 100 bar.

The Koch reaction can occur at double bonds where at least one carbon ofthe double bond is di-substituted to form a "neo" acid or ester ##STR1##(where R' and R" are not hydrogen).

The Koch reaction can also occur when both carbons are monosubstitutedor one is monosubstituted and one is unsubstituted to form an "iso" acid(i.e. --RHC--COOR). Bahrmann et al. discloses isobutylene converted toisobutyric acid via a Koch-type reaction.

U.S. Pat. No. 283 1877 discloses a multi-phase, acid catalyzed, two-stepprocess for the carboxylation of olefins with carbon monoxide.

Complexes of mineral acids in water with BF₃ have been studied tocarboxylate olefins. U.S. Pat. No. 3349107 discloses processes which useless than a stoichiometric amount of acid as a catalyst. Examples ofsuch complexes are H₂ O.BF₃.H₂ O, H₃ PO₄.BF₃.H₂ O and HF.BF₃.H₂ O.

EP-A-0148592 relates to the production of carboxylic acid esters and/orcarboxylic acids by catalyzed reaction of a polymer having carbon-carbondouble bonds, carbon monoxide and either water or an alcohol, optionallyin the presence of oxygen. The catalysts are metals such as palladium,rhodium, ruthenium, iridium, and cobalt in combination with a coppercompound, in the presence of a protonic acid such as hydrochloric acid.A preferred polymer is polyisobutene, which may have at least 80% of itscarbon-carbon double bonds in the form of terminal double bonds. Liquidpolyisobutene having a number average molecular weight in the range offrom 200 to 2,500, preferably up to 1,000 are described.

U.S. Pat. 4927892 relates to reacting a polymer or copolymer of aconjugated diene, at least part of which is formed by 1,2polymerization, with carbon monoxide and water and/or alcohol in thepresence of a catalyst prepared by combining a palladium compound,certain ligands and/or acid except hydrohalogenic acids having a pKa ofless than 2. Useful Lewis acids include BF₃.

Although there are disclosures in the art of olefinic hydrocarbonsfunctionalized at the carbon-carbon double bond to form a carboxylicacid or derivative thereof via Koch-type chemistry, there is nodisclosure that polymers containing carbon-carbon double bonds,including terminal olefinic bonds, either secondary or tertiary typeolefinic bonds, could be successfully reacted via the Koch mechanism.Additionally, it has been found that the process of the presentinvention is particularly useful to make neo acid and neo esterfunctionalized polymer. Known catalysts used to carboxylate lowmolecular weight olefinic hydrocarbons by the Koch mechanism were foundto be unsuitable for use with polymeric material. Specific catalystshave been found which can result in the formation of a carboxylic acidor ester at a carbon-carbon double bond of a polymer. Koch chemistryaffords the advantage of the use of moderate temperatures and pressures,by using highly acidic catalysts and/or careful control ofconcentrations.

Other dispersants comprise polyamine reactants with two or more primarynitrogens. Reactions with ester and acids are normally conducted withstoichiometries of carbonyl to primary amine close to 1.0 or even higherto prevent significant amounts of free amine from being left unreactedin the mixture. This approach results in dispersants containing multiplepolymer branches per molecule with high molecular weights and highviscosities. Furthermore, as the molecular weight of the polymer isincreased, the polar segment of the dispersant becomes the limitingfactor in dispersancy performance with polyamines of the prior art suchas tetraethylenepentamine.

SUMMARY OF THE INVENTION

The present invention is a low viscosity dispersant derived from apolyamine having one primary amino group and 1-10 secondary or tertiaryamino groups. The low viscosity dispersant is derived from reaction of ahydrocarbon functionalized by groups of the formula --CO--Y--R³ whereinY is O or S, R³ is H or hydrocarbyl, and --Y--R³ has a pKa<12, with apolyamine having one primary amino group and 1-10 secondary or tertiaryamino groups.

The present invention relates to a functionalized hydrocarbon polymerwherein the polymer backbone has Mn≧500, functionalization is by groupsof the formula:

    --CO--Y--R.sup.3

wherein Y is O or S, and either R³ is H, hydrocarbyl and at least 50mole % of the functional groups are attached to a tertiary carbon atomof the polymer backbone or R³ is aryl, substituted aryl or substitutedhydrocarbyl.

Thus the functionalized polymer may be depicted by the formula:

    POLY--(CR.sup.1 R.sup.2 --CO--Y--R.sup.3).sub.n            (I)

wherein POLY is a hydrocarbon polymer backbone having a number averagemolecular weight of at least 500, n is a number greater than 0, R¹, R²and R³ may be the same or different and are each H, hydrocarbyl with theproviso that either R¹ and R² are selected such that at least 50 mole %of the --CR¹ R² groups wherein both R¹ and R² are not H, or R³ is arylsubstituted aryl or substituted hydrocarbyl.

As used herein the term "hydrocarbyl" denotes a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character within the context of this inventionand includes polymeric hydrocarbyl radicals. Such radicals include thefollowing:

(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted aromatic, aromatic-substituted aliphatic andalicyclic radicals, and the like, as well as cyclic radicals wherein thering is completed through another portion of the molecule (that is, thetwo indicated substituents may together form a cyclic radical). Suchradicals are known to those skilled in the art; examples include methyl,ethyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl,eicosyl, cyclohexyl, phenyl and naphthyl (all isomers being included).

(2) Substituted hydrocarbon groups; that is, radicals containingnon-hydrocarbon substituents which, in the context of this invention, donot alter predominantly hydrocarbon character of the radical. Thoseskilled in the art will be aware of suitable substituents (e.g., halo,hydroxy, alkoxy, carbalkoxy, nitro, alkylsulfoxy).

(3) Hetero groups; that is, radicals which, while predominantlyhydrocarbon in character within the context of this invention, containatoms other than carbon present in a chain or ring otherwise composed ofcarbon atoms. Suitable hetero atoms will be apparent to those skilled inthe art and include, for example, nitrogen particularly non-basicnitrogen which would deactivate the Koch catalyst, oxygen and sulfur.

In general, no more than about three substituents or hetero atoms, andpreferably no more than one, will be present for each 10 carbon atoms inthe hydrocarbon-based radical. Polymeric hydrocarbyl radicals are thosederived from hydrocarbon polymers, which may be substituted and/orcontain hetero atoms provided that they remain predominantly hydrocarbonin character. The functionalized polymer may be derived from ahydrocarbon polymer comprising non-aromatic carbon-carbon double bond,also referred to as an olefinically unsaturated bond, or an ethylenicdouble bond. The polymer is functionalized at that double bond via aKoch reaction to form the carboxylic acid, carboxylic ester or thio acidor thio ester.

Koch reactions have not heretofore been applied to polymers havingnumber average molecular weights greater than 500. The hydrocarbonpolymer preferably has Mn greater than 1,000. In the Koch process apolymer having at least one ethylenic double bond is contacted with anacid catalyst and carbon monoxide in the presence of a nucleophilictrapping agent such as water or alcohol. The catalyst is preferably aclassical Broensted acid or Lewis acid catalyst. These catalysts aredistinguishable from the transition metal catalysts of the typedescribed in the prior art. The Koch reaction, as applied in the processof the present invention, may result in good yields of functionalizedpolymer, even 90 mole % or greater.

POLY, in general formula I, represents a hydrocarbon polymer backbonehaving Mn of at least 500. Mn may be determined by available techniquessuch as gel permeation chromatography (GPC). POLY is derived fromunsaturated polymer.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The polymers which are useful in the present invention are polymerscontaining at least one carbon-carbon double bond (olefinic orethylenic) unsaturation. Thus, the maximum number of functional groupsper polymer chain is limited by the number of double bonds per chain.Such polymers have been found to be receptive to Koch mechanisms to formcarboxylic acids or derivatives thereof, using the catalysts andnucleophilic trapping agents of the present invention.

Useful polymers in the present invention include polyalkenes includinghomopolymer, copolymer (used interchangeably with interpolymer) andmixtures. Homopolymers and interpolymers include those derived frompolymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2to about 6 carbon atoms.

Particular reference is made to the alpha olefin polymers made usingorgano metallic coordination compounds. A particularly preferred classof polymers are ethylene alpha olefin copolymers such as those disclosedin U.S. Pat. No. 5017299. The polymer unsaturation can be terminal,internal or both. Preferred polymers have terminal unsaturation,preferably a high degree of terminal unsaturation. Terminal unsaturationis the unsaturation provided by the last monomer unit located in thepolymer. The unsaturation can be located anywhere in this terminalmonomer unit. Terminal olefinic groups include vinylidene unsaturation,R^(a) R^(b) C═CH² ; trisubstituted olefin unsaturation, R^(a) R^(b)C═CR^(c) H; vinyl unsaturation, R^(a) HC═CH² ; 1,2-disubstitutedterminal unsaturation, R^(a) HC═CHR^(b) ; and tetra-substituted terminalunsaturation, R^(a) R^(b) C═CR^(c) R^(d). At least one of R^(a) andR^(b) is a polymeric group of the present invention, and the remainingR^(b), R^(c) and R^(d) are hydrocarbon groups as defined with respect toR, R¹, R², and R³ above.

Low molecular weight polymers, also referred to herein as dispersantrange molecular weight polymers, are polymers having Mn less than20,000, preferably 500 to 20,000 (e.g. 1,000 to 20,000), more preferably1,500 to 10,000 (e.g. 2,000 to 8,000) and most preferably from 1,500 to5,000. The number average molecular weights are measured by vapor phaseosmometry. Low molecular weight polymers are useful in formingdispersants for lubricant additives. Medium molecular weight polymersMn's ranging from 20,000 to 200,000, preferably 25,000 to 100,000; andmore preferably, from 25,000 to 80000 are useful for viscosity indeximprovers for lubricating oil compositions, adhesive coatings,tackifiers and sealants. The medium Mn can be determined by membraneosmometry.

The higher molecular weight materials have Mn of greater than about200,000 and can range to 15,000,000 with specific embodiments of 300,000to 10,000,000 and more specifically 500,000 to 2,000,000. These polymersare useful in polymeric compositions and blends including elastomericcompositions. Higher molecular weight materials having Mn's of from20,000 to 15,000,000 can be measured by gel permeation chromatographywith universal calibration, or by light scattering. The values of theratio Mw/Mn, referred to as molecular weight distribution, (MWD) are notcritical. However, a typical minimum Mw/Mn value of about 1.1-2.0 ispreferred with typical ranges of about 1.1 up to about 4.

The olefin monomers are preferably polymerizable terminal olefins; thatis, olefins characterized by the presence in their structure of thegroup --R--C═CH₂, where R is H or a hydrocarbon group. However,polymerizable internal olefin monomers (sometimes referred to in thepatent literature as medial olefins) characterized by the presencewithin their structure of the group: ##STR2## can also be used to formthe polyalkenes. When internal olefin monomers are employed, theynormally will be employed with terminal olefins to produce polyalkeneswhich are interpolymers. For this invention, a particular polymerizedolefin monomer which can be classified as both a terminal olefin and aninternal olefin, will be deemed a terminal olefin. Thus, pentadiene-1,3(i.e., piperylene) is deemed to be a terminal olefin.

While the polyalkenes generally are hydrocarbon polyalkenes, they cancontain substituted hydrocarbon groups such as lower alkoxy, lower alkylmercapto, hydroxy, mercapto, and carbonyl, provided the non-hydrocarbonmoieties do not substantially interfere with the functionalization orderivatization reactions of this invention. When present, suchsubstituted hydrocarbon groups normally will not contribute more thanabout 10% by wt. of the total weight of the polyalkenes. Since thepolyalkene can contain such non-hydrocarbon substituent, it is apparentthat the olefin monomers from which the polyalkenes are made can alsocontain such substituents. As used herein, the term "lower" when usedwith a chemical group such as in "lower alkyl" or "lower alkoxy" isintended to describe groups having up to seven carbon atoms.

The polyalkenes may include aromatic groups and cycloaliphatic groupssuch as would be obtained from polymerizable cyclic olefins orcycloaliphatic substituted-polymerizable acrylic olefins. There is ageneral preference for polyalkenes free from aromatic and cycloaliphaticgroups (other than the diene styrene interpolymer exception alreadynoted). There is a further preference for polyalkenes derived fromhomopolymers and interpolymers of terminal hydrocarbon olefins of 2 to16 carbon atoms. This further preference is qualified by the provisothat, while interpolymers of terminal olefins are usually preferred,interpolymers optionally containing up to about 40% of polymer unitsderived from internal olefins of up to about 16 carbon atoms are alsowithin a preferred group. A more preferred class of polyalkenes arethose selected from the group consisting of homopolymers andinterpolymers of terminal olefins of 2 to 6 carbon atoms, morepreferably 2 to 4 carbon atoms. However, another preferred class ofpolyalkenes are the latter, more preferred polyalkenes optionallycontaining up to about 25% of polymer units derived from internalolefins of up to about 6 carbon atoms.

Specific examples of terminal and internal olefin monomers which can beused to prepare the polyalkenes according to conventional, well-knownpolymerization techniques include ethylene; propylene; butene-1;butene-2; isobutene; pentene-1; etc.; propylene-tetramer; diisobutylene;isobutylene trimer; butadiene-1,2; butadiene-1,3; pentadiene-1,2;pentadiene-1,3; etc.

Useful polymers include alpha-olefin homopolymers and interpolymers, andethylene alpha-olefin copolymers and terpolymers. Specific examples ofpolyalkenes include polypropylenes, polybutenes, ethylene-propylenecopolymers, ethylene-butene copolymers, propylene-butene copolymers,styrene-isobutene copolymers, isobutene-butadiene-1,3 copolymers, etc.,and terpolymers of isobutene, styrene and piperylene and copolymer of80% of ethylene and 20% of propylene. A useful source of polyalkenes arethe poly(isobutene)s obtained by polymerization of C₄ refinery streamhaving a butene content of about 35 to about 75% by wt., and anisobutene content of about 30 to about 60% by wt., in the presence of aLewis acid catalyst such as aluminum trichloride or boron trifluoride.Also useful are the high molecular weight poly-n-butenes of U.S. Ser.No. 992871 filed Dec. 17, 1992. A preferred source of monomer for makingpoly-n-butenes is petroleum feedstreams such as Raffinate II. Thesefeedstocks are disclosed in the art such as in U.S. Pat. No. 4952739.

Ethylene Alpha-Olefin Copolymer

Preferred polymers are polymers of ethylene and at least onealpha-olefin having the formula H₂ C═CHR₄ wherein R⁴ is straight chainor branched chain alkyl radical comprising 1 to 18 carbon atoms andwherein the polymer contains a high degree of terminal ethenylideneunsaturation. Preferably R⁴ in the above formula is alkyl of from 1 to 8carbon atoms and more preferably is alkyl of from 1 to 2 carbon atoms.Therefore, useful comonomers with ethylene in this invention includepropylene, 1-butene, hexene-1, octene-1, etc., and mixtures thereof(e.g. mixtures of propylene and 1-butene, and the like). Preferredpolymers are copolymers of ethylene and propylene and ethylene andbutene-1.

The molar ethylene content of the polymers employed is preferably in therange of between about 20 and about 80%, and more preferably betweenabout 30 and about 70%. When butene-1 is employed as comonomer withethylene, the ethylene content of such copolymer is most preferablybetween about 20 and about 45 wt. %, although higher or lower ethylenecontents may be present. The most preferred ethylene-butene-1 copolymersare disclosed in U.S. Ser. No. 992192, filed Dec. 17, 1992. Thepreferred method for making low molecular weight ethylene/α-olefincopolymer is described in U.S. Ser. No. 992690, filed Dec. 17, 1992.

Preferred ranges of number average molecular weights of polymer for useas precursors for dispersants are from 500 to 10,000, preferably from1,000 to 8,000, most preferably from 2,500 to 6,000. A convenient methodfor such determination is by size exclusion chromatography (also knownas gel permeation chromatography (GPC)) which additionally providesmolecular weight distribution information. Such polymers generallypossess an intrinsic viscosity (as measured in tetralin at 135° C.) ofbetween 0.025 and 0.6 dl/g, preferably between 0.05 and 0.5 dl/g, mostpreferably between 0.075 and 0.4 dl/g. These polymers preferably exhibita degree of crystallinity such that, when grafted, they are essentiallyamorphous.

The preferred ethylene alpha-olefin polymers are further characterizedin that up to about 95% and more of the polymer chains possess terminalvinylidene-type unsaturation. Thus, one end of such polymers will be ofthe formula POLY-C(R¹¹) ═CH₂ wherein R¹¹ is C₁ to C₁₈ alkyl, preferablyC₁ to C₈ alkyl, and more preferably methyl or ethyl and wherein POLYrepresents the polymer chain. A minor amount of the polymer chains cancontain terminal ethenyl unsaturation, i.e. POLY-CH═CH₂, and a portionof the polymers can contain internal monounsaturation, e.g.POLY--CH═CH(R¹¹), wherein R¹¹ is as defined above.

The preferred ethylene alpha-olefin polymer comprises polymer chains, atleast about 30% of which possess terminal vinylidene unsaturation.Preferably at least about 50%, more preferably at least about 60%, andmost preferably at least about 75% (e.g. 75 to 98%), of such polymerchains exhibit terminal vinylidene unsaturation. The percentage ofpolymer chains exhibiting terminal vinylidene unsaturation may bedetermined by FTIR spectroscopic analysis, titration, HNMR, or C₁₃ NMR.

The polymers can be prepared by polymerizing monomer mixtures comprisingethylene with other monomers such as alpha-olefins, preferably from 3 to4 carbon atoms in the presence of a metallocene catalyst systemcomprising at least one metallocene (e.g., a cyclopentadienyl-transitionmetal compound) and an activator, e.g. alumoxane compound. The comonomercontent can be controlled through selection of the metallocene catalystcomponent and by controlling partial pressure of the monomers.

The polymer for use in the present invention can include block andtapered copolymers derived from monomers comprising at least oneconjugated diene with at least monovinyl aromatic monomer, preferablystyrene. Such polymers should not be completely hydrogenated so that thepolymeric composition contains olefinic double bonds, preferably atleast one bond per molecule. The present invention can also include starpolymers as disclosed in patents such as U.S. Pat. Nos. 5,070,131;4,108,9945; 3,711,406; and 5,049,294.

The letter n is greater than 0 and represents the functionality (F) oraverage number of functional groups per polymer chain. Thus,functionality can be expressed as the average number of moles offunctional groups per "mole of polymer". It is to be understood that theterm "mole of polymer" includes both functionalized and unfunctionalizedpolymer, so that F which corresponds to n of Formula (I). Thefunctionalized polymer will include molecules having no functionalgroups. Specific preferred embodiments of n include 1≧n>0; 2≧n>1;and n2.n can be determined by C¹³ NMR. The optimum number of functional groupsneeded for desired performance will typically increase with numberaverage molecular weight of the polymer. The maximum value of n will bedetermined by the number of double bonds per polymer chain in theunfunctionalized polymer.

In specific and preferred embodiments the "leaving group" (--YR³) has apKa of less than or equal to 12, preferably less than 10, and morepreferably less than 8. The pKa is determined from the correspondingacidic species HY-R³ in water at room temperature. Where the leavinggroup is a simple acid or alkyl ester, the functionalized polymer isvery stable especially as the % neo substitution increases. The presentinvention is especially useful to make "neo" functionalized which aregenerally more stable and less labile than iso structures. In preferredembodiments the polymer can be at least 60, more preferably at least 80mole % neofunctionalized. The polymer can be greater than 90, or 99 andeven about 100 mole % neo. In one preferred composition the polymerdefined by formula (I), Y is O (oxygen), R¹ and R² can be the same ordifferent and are selected from H, a hydrocarbyl group, and a polymericgroup.

In another preferred embodiment Y is O or S, R¹ and R² can be the sameor different and are selected from H, a hydrocarbyl group a substitutedhydrocarbyl group and a polymeric group, and R³ is selected from asubstituted hydrocarbyl group, an aromatic group and a substitutedaromatic group. This embodiment is generally more reactive towardsderivatization with amines and alcohol compounds especially where the R³substituent contains electron withdrawing species. It has been foundthat in this embodiment, a preferred leaving group, HYR³, has a pKa ofless than 12, preferably less than 10 and more preferably 8 or less. pKavalues can range typically from 5 to 12, preferably from 6 to 10, andmost preferably from 6 to 8. The pKa of the leaving group determines howreadily the system will react with derivatizing compounds to producederivatized product.

In a particularly preferred composition, R³ is represented by theformula: ##STR3## wherein X, which may be the same or different, is anelectron withdrawing substituent, T, which may be the same or different,represents a non-electron withdrawing substituent (e.g. electrondonating), and m and p are from 0 to 5 with the sum of m and p beingfrom 0 to 5. More preferably, m is from 1 to 5 and preferably 1 to 3. Ina particularly preferred embodiment X is selected from a halogen,preferably F or Cl, CF₃, cyano groups and nitro groups and p=0. Apreferred R³ is derived from 2,4-dichlorophenol.

The composition of the present invention includes derivatized polymerwhich is the reaction product of the Koch functionalized polymer and aderivatizing compound. Preferred derivatizing compounds includenucleophilic reactant compounds including amines, alcohols,amino-alcohols, metal reactant compounds and mixtures thereof.Derivatized polymer will typically contain at least one of the followinggroups: amide, imide, oxazoline, and ester, and metal salt. Thesuitability for a particular end use may be improved by appropriateselection of the polymer Mn and functionality used in the derivatizedpolymer as discussed hereinafter.

The Koch reaction permits controlled functionalization of unsaturatedpolymers. When a carbon of the carbon-carbon double bond is substitutedwith hydrogen, it will result in an "iso" functional group, i.e. one ofR¹ or R² of Formula I is H; or when a carbon of the double bond is fullysubstituted with hydrocarbyl groups it will result in an "neo"functional group, i.e. both R¹ or R² of Formula I are non-hydrogengroups.

Polymers produced by processes which result in a terminally unsaturatedpolymer chain can be functionalized to a relatively high yield inaccordance with the process of the present invention. It has been foundthat the neo acid functionalized polymer can be derivatized to arelatively high yield.

The Koch process also makes use of relatively inexpensive materialsi.e., carbon monoxide at relatively low temperatures and pressures. Alsothe leaving group --YR³ can be removed and recycled upon derivatizingthe Koch functionalized polymer with amines or alcohols.

The functionalized or derivatized polymers of the present invention areuseful as lubricant additives such as dispersants, viscosity improversand multifunctional viscosity improvers.

The present invention includes oleaginous compositions comprising theabove functionalized, and/or derivatized polymer. Such compositionsinclude lubricating oil compositions and concentrates. The inventionalso provides a process which comprises the step of catalyticallyreacting in admixture:

(a) at least one hydrocarbon polymer having a number average molecularweight of at least about 500, and an average of at least one ethylenicdouble bond per polymer chain;

(b) carbon monoxide,

(c) at least one acid catalyst, and

(d) a nucleophilic trapping agent selected from the group consisting ofwater, hydroxy-containing compounds and thiol-containing compounds, thereaction being conducted a) in the absence of reliance on transitionmetal as a catalyst; or b) with at least one acid catalyst having aHammett acidity of less than -7; or c) wherein functional groups areformed at least 40 mole % of the ethylenic double bonds; or d) whereinthe nucleophilic trapping agent has a pKa of less than 12.

The process of the present invention relates to a polymer having atleast one ethylenic double bond reacted via a Koch mechanism to formcarbonyl or thio carbonyl group-containing compounds, which maysubsequently be derivatized. The polymers react with carbon monoxide inthe presence of an acid catalyst or a catalyst preferably complexed withthe nucleophilic trapping agent. A preferred catalyst is BF₃ andpreferred catalyst complexes include BF₃.H₂ O and BF₃ complexed with2,4-dichlorophenol. The starting polymer reacts with carbon monoxide atpoints of unsaturation to form either iso- or neo-acyl groups with thenucleophilic trapping agent, e.g. with water, alcohol (preferably asubstituted phenol) or thiol to form respectively a carboxylic acid,carboxylic ester group, or thio ester.

In a preferred process, at least one polymer having at least onecarbon-carbon double bond is contacted with an acid catalyst or catalystcomplex having a Hammett Scale acidity value of less than -7, preferablyfrom -8.0 to -11.5 and most preferably from -10 to -11.5. Withoutwishing to be bound by any particular theory, it is believed that acarbenium ion may form at the site of one of carbon-carbon double bonds.The carbenium ion may then react with carbon monoxide to form an acyliumcation. The acylium cation may react with at least one nucleophilictrapping agent as defined herein.

At least 40 mole %, preferably at least 50 mole %, more preferably atleast 80 mole %, and most preferably 90 mole % of the polymer doublebonds will react to form acyl groups wherein the non-carboxyl portion ofthe acyl group is determined by the identity of the nucleophilictrapping agent, i.e. water forms acid, alcohol forms acid ester andthiol forms thio ester. The polymer functionalized by the recitedprocess of the present invention can be isolated using fluoride salts.The fluoride salt can be selected from the group consisting of ammoniumfluoride, and sodium fluoride.

Preferred nucleophilic trapping agents are selected from the groupconsisting of water, monohydric alcohols, polyhydric alcoholshydroxyl-containing aromatic compounds and hetero substituted phenoliccompounds. The catalyst and nucleophilic trapping agent can be addedseparately or combined to form a catalytic complex.

Following is an example of a terminally unsaturated polymer reacted viathe Koch mechanism to form an acid or an ester. The polymer is contactedwith carbon monoxide or a suitable carbon monoxide source such as formicacid in the presence of an acidic catalyst. The catalyst contributes aproton to the carbon-carbon double bond to form a carbenium ion. This isfollowed by addition of CO to form an acylium ion which reacts with thenucleophilic trapping agent. POLY, Y, R¹, R² and R³ are defined asabove. ##STR4##

The Koch reaction is particularly useful to functionalize poly(alphaolefins) and ethylene alpha olefin copolymers formed usingmetallocene-type catalysts. These polymers contain terminal vinylidenegroups. There is a tendency for such terminal groups to predominate andresult in neo-type (tertiary) carbenium ions. In order for the carbeniumion to form, the acid catalyst is preferably relatively strong. However,the strength of the acid catalyst is preferably balanced againstdetrimental side reactions which can occur when the acid is too strong.

The Koch catalyst can be employed by preforming a catalyst complex withthe proposed nucleophilic trapping agent or by adding the catalyst andtrapping agent separately to the reaction mixture. This later embodimenthas been found to be a particular advantage since it eliminates the stepof making the catalyst complex. The following are examples of suitableacidic catalyst and catalyst complex materials with their respectiveHammett Scale Value acidity: 60% H₂ SO₄, -4.32; BF₃.3H₂ O, -4.5; BF₃.2H₂O, -7.0; WO₃ /Al₂ O₃, less than -8.2; SiO₂ /Al₂ O₃, less than -8.2; HF,-10.2; BF₃.H₂ O, -11.4 to -11.94; ZrO₂ less than -12.7; SiO₂ /Al₂ O₃,-12.7 to 13.6; AlCl₃, -13.16 to -13.75; AlCl₃ /CuSO₄, -13.75 to -14.52.

It has been found that BF₃.2H₂ O is ineffective at functionalizingpolymer through a Koch mechanism ion with polymers. In contrast, BF3.H₂O resulted in high yields of carboxylic acid for the same reaction. Theuse of H₂ SO₄ as a catalyst involves control of the acid concentrationto achieve the desired Hammett Scale Value range. Preferred catalystsare H₂ SO₄ and BF₃ catalyst systems.

Suitable BF₃ catalyst complexes for use in the present invention can berepresented by the formula:

    BF.sub.3.xHOR

wherein R can represent hydrogen, hydrocarbyl (as defined below inconnection with R')--CO--R', --SO₂ --R', --PO--(OH)₂, and mixturesthereof wherein R' is hydrocarbyl, typically alkyl, e.g., C₁ to C₂₀alkyl, and, e.g., C₆ to C₁₄ aryl, aralkyl, and alkaryl, and x is lessthan 2.

Following reaction with CO, the reaction mixture is further reacted withwater or another nucleophilic trapping agent such as an alcohol orphenolic, or thiol compound. The use of water releases the catalyst toform an acid. The use of hydroxy trapping agents releases the catalystto form an ester, the use of a thiol releases the catalyst to form athio ester.

Koch product, also referred to herein as functionalized polymer,typically will be derivatized as described hereinafter. Derivatizationreactions involving ester functionalized polymer will typically have todisplace the alcohol derived moiety therefrom. Consequently, the alcoholderived portion of the Koch functionalized polymer is sometimes referredto herein as a leaving group. The ease with which a leaving group isdisplaced during derivatization will depend on its acidity, i.e. thehigher the acidity the more easily it will be displaced. The acidity inturn of the alcohol is expressed in terms of its pKa.

Preferred nucleophilic trapping agents include water and hydroxy groupcontaining compounds. Useful hydroxy trapping agents include aliphaticcompounds such as monohydric and polyhydric alcohols or aromaticcompounds such as phenols and naphthols. The aromatic hydroxy compoundsfrom which the esters of this invention may be derived are illustratedby the following specific example: phenol, -naphthol, cresol,resorcinol, catechol, 2-chlorophenol. Particularly preferred is2,4-dichlorophenol. The alcohols preferably can contain up to about 40aliphatic carbon atoms. They may be monohydric alcohols such asmethanols, ethanol, benzyl alcohol, 2-methylcyclohexanol,beta-chloroethanol, monomethyl ether of ethylene glycol, etc. Thepolyhydric alcohols preferably contain from 2 to about 5 hydroxyradicals; e.g., ethylene glycol, diethylene glycol. Other usefulpolyhydric alcohols include glycerol, monomethyl ether of glycerol, andpentaerythritol. Useful unsaturated alcohols include allyl alcohol, andpropargyl alcohol. Particularly preferred alcohols include those havingthe formula R*₂ CHOH where an R* is independently hydrogen, an alkyl,aryl, hydroxyalkyl, or cycloalkyl. Specific alcohols include alkanolssuch as methanol, ethanol, etc. Also preferred useful alcohols includearomatic alcohols, phenolic compounds and polyhydric alcohols as well asmonohydric alcohols such as 1,4-butanediol.

It has been found that neo-acid ester functionalized polymer isextremely stable due, it is believed, to stearic hindrance.Consequently, the yield of derivatized polymer obtainable therefrom willvary depending on the ease with which a derivatizing compound candisplace the leaving group of the functionalized polymer. The mostpreferred alcohol trapping agents may be obtained by substituting aphenol with at least one electron withdrawing substituent such that thesubstituted phenol possesses a pKa within the above described preferredpKa ranges. In addition, phenol may also be substituted with at leastone non-electron withdrawing substituent (e.g., electron donating),preferably at positions meta to the electron withdrawing substituent toblock undesired alkylation of the phenol by the polymer during the Kochreaction. This further improves yield to desired ester functionalizedpolymer.

Accordingly, and in view of the above, the most preferred trappingagents are phenolic and substituted phenolic compounds represented bythe formula: ##STR5## wherein X, which may be the same or different, isan electron withdrawing substituent, and T which may be the same ordifferent is a non-electron withdrawing group; m and p are from 0 to 5with the sum of m and p being from 0 to 5, and m is preferably from 1 to5, and more preferably, m is 1 or 2. X is preferably a group selectedfrom halogen, cyano, and nitro, preferably located at the 2- and/or4-position, and T is a group selected from hydrocarbyl, and hydroxygroups and p is 1 or 2 with T preferably being located at the 4 and/or 6position. More preferably X is selected from Cl, F, Br, cyano or nitrogroups and m is preferably from 1 to 5, more preferably from 1 to 3, yetmore preferably 1 to 2, and most preferably 2 located at the 2 and 4locations relative to --OH.

The relative amounts of reactants and catalyst, and the conditionscontrolled in a manner sufficient to functionalize typically at leastabout 40, preferably at least about 80, more preferably at least about90 and most preferably at least about 95 mole % of the carbon-carbondouble bonds initially present in the unfunctionalized polymer. Theamount of H₂ O, alcohol, or thiol used is preferably at least thestoichiometric amount required to react with the acylium cations. It ispreferred to use an excess of alcohol over the stoichiometric amount.The alcohol performs the dual role of reactant and diluent for thereaction. However, the amount of the alcohol or water used should besufficient to provide the desired yield yet at the same time not dilutethe acid catalyst so as to adversely affect the Hammett Scale Valueacidity.

The polymer added to the reactant system can be in a liquid phase.Optionally, the polymer can be dissolved in an inert solvent. The yieldcan be determined upon completion of the reaction by separating polymermolecules which contain acyl groups which are polar and hence can easilybe separated from unreacted non-polar compounds. Separation can beperformed using absorption techniques which are known in the art. Theamount of initial carbon-carbon double bonds and carbon-carbon doublebonds remaining after the reaction can be determined by C¹³ NMRtechniques.

In accordance with the process, the polymer is heated to a desiredtemperature range which is typically between -20° C. to 200° C.,preferably from 0° C. to 80° C. and more preferably from 40° C. to 65°C. Temperature can be controlled by heating and cooling means applied tothe reactor. Since the reaction is exothermic usually cooling means arerequired. Mixing is conducted throughout the reaction to assure auniform reaction medium.

The catalyst (and nucleophilic trapping agent) can be prereacted to forma catalyst complex or are charged separately in one step to the reactorto form the catalyst complex in situ at a desired temperature andpressure, preferably under nitrogen. In a preferred system thenucleophilic trapping agent is a substituted phenol used in combinationwith BF₃. The reactor contents are continuously mixed and then rapidlybrought to a desired operating pressure using a high pressure carbonmonoxide source. Useful pressures can be up to 138,000 kPa (20,000psig), and typically will be at least 2,070 kPa (300 psig), preferablyat least 5,520 kPa (800 psig), and most preferably at least 6,900 kPa(1,000 psig), and typically will range from 3,450 to 34,500 kPa (500 to5,000 psig) preferably from 4,485 to 20,700 kPa (650 to 3,000 psig) andmost preferably from 4,485 to 13,800 kPa (650 to 2,000 psig). The carbonmonoxide pressure may be reduced by adding a catalyst such as a coppercompound. The catalyst to polymer volume ratio can range from 0.25 to 4,preferably 0.5 to 2 and most preferably 0.75 to 1.3.

Preferably, the polymer, catalyst, nucleophilic trapping agent and COare fed to the reactor in a single step. The reactor contents are thenheld for a desired amount of time under the pressure of the carbonmonoxide. The reaction time can range up to 5 hrs. and typically 0.5 to4 and more typically from 1 to 2 hrs. The reactor contents can then bedischarged and the product which is a Koch functionalized polymercomprising either a carboxylic acid or carboxylic ester or thiol esterfunctional groups separated. Upon discharge, any unreacted CO can bevented off. Nitrogen can be used to flush the reactor and the vessel toreceive the polymer.

Depending on the particular reactants employed, the functionalizedpolymer containing reaction mixture may be a single phase, a combinationof a partitionable polymer and acid phase or an emulsion with either thepolymer phase or acid phase being the continuous phase. Upon completionof the reaction, the polymer is recovered by suitable means. When themixture is an emulsion, a suitable means can be used to separate thepolymer. A preferred means is the use of fluoride salts, such as sodiumor ammonium fluoride in combination with an alcohol such as butanol ormethanol to neutralize the catalyst and phase separate the reactioncomplex. The fluoride ion helps trap the BF₃ complexed to thefunctionalized polymer and helps break emulsions generated when thecrude product is washed with water. Alcohols such as methanol andbutanol and commercial demulsifiers also help to break emulsionsespecially in combination with fluoride ions. Preferably, nucleophilictrapping agent is combined with the fluoride salt and alcohols when usedto separate polymers. The presence of the nucleophilic trapping agent asa solvent minimizes transesterification of the functionalized polymer.Where the nucleophilic trapping agent has a pKa of less than 12 thefunctionalized polymer can be separated from the nucleophilic trappingagent and catalyst by depressurization and distillation. It has beenfound that where the nucleophilic trapping agent has lower pKa's, thecatalyst, i.e. BF₃ releases more easily from the reaction mixture.

As indicated above, polymer which has undergone the Koch reaction isalso referred to herein as functionalized polymer. Thus, afunctionalized polymer comprises molecules which have been chemicallymodified by at least one functional group so that the functionalizedpolymer is (a) capable of undergoing further chemical reaction (e.g.derivatization) or (b) has desirable properties, not otherwise possessedby the polymer alone, absent such chemical modification.

It will be observed from the discussion of formula I that the functionalgroup is characterized as being represented by the parentheticalexpression ##STR6## which expression contains the acyl group ##STR7## Itwill be understood that while the ##STR8## moiety is not added to thepolymer in the sense of being derived from a separate reactant it isstill referred to as being part of the functional group for ease ofdiscussion and description. Strictly speaking, it is the acyl groupwhich constitutes the functional group, since it is this group which isadded during chemical modification. Moreover, R₁ and R₂ represent groupsoriginally present on, or constituting part of, the 2 carbons bridgingthe double bond before functionalization. However, R₁ and R₂ wereincluded within the parenthetical so that neo acyl groups could bedifferentiated from iso acyl groups in the formula depending on theidentity of R₁ and R₂.

Typically, where the end use of the polymer is for making dispersant,e.g. as derivatized polymer, the polymer will possess dispersant rangemolecular weights (Mn) as defined hereinafter and the functionality willtypically be significantly lower than for polymer intended for makingderivatized multifunctional V.I. improvers, where the polymer willpossess viscosity modifier range molecular weights (Mn) as definedhereinafter. Accordingly, while any effective functionality can beimparted to functionalized polymer intended for subsequentderivatization, it is contemplated that such functionalities, expressedas F, for dispersant end uses, are typically not greater than about 3,preferably not greater than about 2, and typically can range from about0.5 to about 3, preferably from 0.8 to about 2.0 (e.g. 0.8 to 1).

Similarly, effective functionalities F for viscosity modifier end usesof derivatized polymer are contemplated to be typically greater thanabout 3, preferably greater than about 5, and typically will range from5 to about 10. End uses involving very high molecular weight polymerscontemplate functionalities which can range typically greater than about20, preferably greater than about 30, and most preferably greater thanabout 40, and typically can range from 20 to 60, preferably from 25 to55 and most preferably from 30 to 50.

U.S. Ser. No. 261,507, Amidation of Ester Functionalized Polymers; U.S.Ser. No. 261,557 Prestripped Polymer Used to Improve Koch ReactionDispersant Additives; U.S. Ser. No. 261,559, Batch Koch CarbonylationProcess; U.S. Ser. No. 261,560, Continuous Process for Production ofFunctionalized Olefins; U.S. Ser. No. 261,554, Lubricating OilDispersants Derived from Heavy Polyamines; and U.S. Ser. No. 261,558,Functionalized Additives Useful In Two-Cycle Engines, all filed Jun. 17,1994, all contain related subject matter as indicated by their titlesand are hereby incorporated by reference in their entirety for allpurposes.

Derivatized Polymers

The functionalized polymer can be used as a dispersant/multifunctionalviscosity modifier if the functional group contains the requisite polargroup. The functional group can also enable the polymer to participatein a variety of chemical reactions. Derivatives of functionalizedpolymers can be formed through reaction of the functional group. Thesederivatized polymers may have the requisite properties for a variety ofuses including use as dispersants and viscosity modifiers. A derivatizedpolymer is one which has been chemically modified to perform one or morefunctions in a significantly improved way relative to theunfunctionalized polymer and/or the functionalized polymer.Representative of such functions, are dispersancy and/or viscositymodification in lubricating oil compositions.

The derivatizing compound typically contains at least one reactivederivatizing group selected to react with the functional groups of thefunctionalized polymers by various reactions. Representative of suchreactions are nucleophilic substitution, transesterification, saltformation, and the like. The derivatizing compound preferably alsocontains at least one additional group suitable for imparting thedesired properties to the derivatized polymer, e.g., polar groups. Thus,such derivatizing compounds typically will contain one or more groupsincluding amine, hydroxy, ester, amide, imide, thio, thioamido,oxazoline, or carboxylate groups or form such groups at the completionof the derivatization reaction.

The derivatized polymers include the reaction product of the aboverecited functionalized polymer with a nucleophilic reactant whichinclude amines, alcohols, amino-alcohols and mixtures thereof to formoil soluble salts, amides, oxazoline, and esters. Alternatively, thefunctionalized polymer can be reacted with basic metal salts to formmetal salts of the polymer. Preferred metals are Ca, Mg, Cu, Zn, Mo, andthe like.

Suitable properties sought to be imparted to the derivatized polymerinclude one or more of dispersancy, multifunctional viscositymodification, antioxidancy, friction modification, antiwear, antirust,seal swell, and the like. The preferred properties sought to be impartedto the derivatized polymer include dispersancy (both mono- and multifunctional) and viscosity modification primarily with attendantsecondary dispersant properties. A multi functional dispersant typicallywill function primarily as a dispersant with attendant secondaryviscosity modification.

While the Koch functionalization and derivatization techniques forpreparing multifunctional viscosity modifiers (also referred to hereinas multi functional viscosity index improvers or MFVI) are the same asfor ashless dispersants, the functionality of a functionalized polymerintended for derivatization and eventual use as an MFVI will becontrolled to be higher than functionalized polymer intended foreventual use as a dispersant. This stems from the difference in Mn ofthe MFVI polymer backbone vs. the Mn of the dispersant polymer backbone.Accordingly, it is contemplated that an MFVI will be derived fromfunctionalized polymer having typically up to about one and at leastabout 0.5 functional groups, (i.e. "n" of formula (I)) for each 20,000,preferably for each 10,000, most preferably for each 5,000 Mn molecularweight segment in the backbone polymer.

Dispersants

Dispersants maintain oil insolubles, resulting from oil use, insuspension in the fluid thus preventing sludge flocculation andprecipitation. Suitable dispersants include, for example, dispersants ofthe ash-producing (also known as detergents) and ashless type, thelatter type being preferred. The derivatized polymer compositions of thepresent invention, can be used as ashless dispersants andmultifunctional viscosity index improvers in lubricant and fuelcompositions.

At least one functionalized polymer is mixed with at least one of amine,alcohol, including polyol, aminoalcohol, etc., to form the dispersantadditives. One class of particularly preferred dispersants are thosederived from the functionalized polymer of the present invention reactedwith (i) hydroxy compound, e.g., a polyhydric alcohol orpolyhydroxy-substituted aliphatic primary amine such as pentaerythritolor trismethylolaminomethane (ii) polyoxyalkylene polyamine, e.g.polyoxypropylene diamine, and/or (iii) polyalkylene polyamine, e.g.,polyethylene polyamine such as tetraethylene pentamine referred toherein as TEPA.

Derivatization by Amine Compounds

Useful amine compounds for derivatizing functionalized polymers compriseat least one amine and can comprise one or more additional amine orother reactive or polar groups. Where the functional group is acarboxylic acid, carboxylic ester or thiol ester, it reacts with theamine to form an amide. Preferred amines are aliphatic saturated amines.Non-limiting examples of suitable amine compounds include:1,2-diaminoethane; 1,3 -diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; etc.

Other useful amine compounds include: alicyclic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines. Mixtures of amine compounds may advantageously beused. Useful amines also include polyoxyalkylene polyamines. Aparticularly useful class of amines are the polyamido and relatedamines.

For the preferred polyamine dispersant of this invention, the novelpreferred compositions allow the benefit of using higher molecularweight backbones without the limitation of low nitrogen content and thedebit of high viscosities.

Polyamines containing one primary amino group and 1-10 secondary ortertiary amino groups are useful. For lube applications polyamines with3-8 secondary or tertiary amino groups are preferred. For fuelapplications polyamines with 1-3 secondary or tertiary amino groups arepreferred. These polyamines may optionally contain oxygen and sulfuratoms as part of the molecule. The amino groups and the oxygen andsulfur are generally separated from each other by hydrocarbylene groupscontaining from 1-6 carbons. The polyamines could contain heterocyclesas part of their structure.

The preferred polyamines contain only one primary amine per molecule.However, as the number of nitrogen atoms in the polyamines increases,some branching could occur giving mixtures of polyamines containingprimarily one amino group with some molecules containing more than oneprimary amino group. To minimize the viscosity of the final product andmaximize the nitrogen content, polyamines with the least amount ofbranching are preferred.

In general these one armed polyamines belong to two groups: (1)nonvolatile and (2) volatile amines. Volatile one armed polyamines areconsidered those polyamines that can be distilled during the strippingstep of the process if any remain unreacted as free amine. Volatileamines can be used in large excess to facilitate the completion of thereaction in the shortest possible time since the unreacted amines can berecovered and reused. The stoichiometry of the nonvolatile amine islimited to about one primary amino group per carbonyl group to avoidresidual unreacted polyamine in the dispersant mixture.

One type of one armed polyamine can be represented by the formula:

    H.sub.2 N(--R.sup.5 --NH--).sub.z --(--R.sup.6 --A--).sub.y --R.sup.7

Wherein:

R⁵ and R⁶ are hydrocarbon groups from one to six carbons.

R⁷ is a hydrocarbyl group containing from one to 40 carbons or aheterocyclic structure containing N, and/or S, and/or O.

A is oxygen or sulfur.

z=1to 10.

y=0to 1.

One method to prepare these one armed polyamines consists of stepwisereaction of known alcohols, mono or polyamines with acrylonitrilefollowed by hydrogenation. The following is a partial list of thesepolyamines: ##STR9## Derivatization by Alcohols

The functionalized polymers of the present invention can be reacted withalcohols, e.g. to form esters. The alcohols may be aliphatic compoundssuch as monohydric and polyhydric alcohols or aromatic compounds such asphenols and naphthols. The aromatic hydroxy compounds from which theesters may be derived are illustrated by the following specificexamples: phenol, beta-naphthol, alpha-naphthol, cresol, resorcinol,catechol, etc. Phenol and alkylated phenols having up to three alkylsubstituents are preferred. The alcohols from which the esters may bederived preferably contain up to about 40 aliphatic carbon atoms. Theymay be monohydric alcohols such as methanols, ethanol, isooctanol, etc.A useful class of polyhydric alcohols are those having at least threehydroxy radicals, some of which have been esterified with amonocarboxylic acid having from about 8 to about 30 carbon atoms, suchas octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoicacid, or tall oil acid.

The esters may also be derived from unsaturated alcohols such as allylalcohol, cinnamyl alcohol, propargyl alcohol. Still another class of thealcohols capable of yielding the esters of this invention comprise theether-alcohols and amino-alcohols including, for example, theoxyalkylene-, oxyarylene-, amino-alkylene-, andamino-arylene-substituted alcohols having one or more oxyalkylene,amino-alkylene or amino-arylene oxyarylene radicals. They areexemplified by Cellosolve, carbitol, phenoxyethanol, etc.

The functionalized polymer of this invention is reacted with thealcohols according to conventional esterification, ortransesterification techniques. This normally involves heating thefunctionalized polymer with the alcohol, optionally in the presence of anormally liquid, substantially inert, organic liquid solvent/diluentand/or in the presence of esterification catalyst.

Derivatization by Reactive Metals/Metal Compounds

Useful reactive metals or reactive metal compounds are those which willform metal salts of the functionalized polymer or metal-containingcomplexes with the functionalized polymer. Metal complexes are typicallyachieved by reacting the functionalized polymers with amines and/oralcohols as discussed above and also with complex forming reactantseither during or subsequent to amination. Complex-forming metalreactants include the nitrates, nitrites, halides, carboxylates, etc.

The appropriate functionalized polymer of this invention can be reactedwith any individual derivatizing compound such as amine, alcohol,reactive metal, reactive metal compound or any combination of two ormore of any of these; that is, for example, one or more amines, one ormore alcohols, one or more reactive metals or reactive metal compounds,or a mixture of any of these. Substantially inert organic liquiddiluents may be used to facilitate mixing, temperature control, andhandling of the reaction mixture.

The reaction products produced by reacting functionalized polymer ofthis invention with derivatizing compounds such as alcohols,nitrogen-containing reactants, metal reactants, and the like will, infact, be mixtures of various reaction products. The functionalizedpolymers themselves can be mixtures of materials. While thefunctionalized polymers themselves possess some dispersantcharacteristics and can be used as dispersant additives in lubricantsand fuels, best results are achieved when at least about 30, preferably,at least about 50, most preferably 100% of the functional groups arederivatized.

Post Treatment

Functionalized and/or derivatized polymers may be post-treated. Theprocesses for post-treating derivatized polymer are analogous to thepost-treating processes used with respect to conventional dispersantsand MFVI's of the prior art. Accordingly, the same reaction conditions,ratio of reactants and the like can be used. Accordingly, derivatizedpolymer can be post-treated with such reagents as urea, thiourea, carbondisulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substitutedsuccinic anhydrides, nitriles, epoxides, boron compounds, phosphoruscompounds or the like. The amine derivatized polymers of the presentinvention as described above can be post-treated, particularly for useas dispersants and viscosity index improvers by contacting said polymerswith one or more post-treating reagents such as boron compounds,nitrogen compounds, phosphorus compounds, oxygen compounds, succinicacids and anhydrides (e.g., succinic anhydride, dodecyl succinicanhydride, and C₁ to C₃₀ hydrocarbyl substituted succinic anhydride),other acids and anhydrides such as maleic and fumaric acids andanhydrides, and esters of the foregoing e.g., methyl maleate. The aminederivatized polymers are preferably treated with boron oxide, boronhalides, boron acid esters or boron ester in an amount to provide from0.1-20.0 atomic proportions of boron per mole of nitrogen composition.Borated derivatized polymer useful as dispersants can contain from 0.05to 2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron based on the total weight ofsaid borated nitrogen-containing dispersant compound.

Treating is readily carried out by adding said boron compound,preferably boric acid usually as a slurry, to said nitrogen compound andheating with stirring at from about 135° C. to 190° C., e.g. 140° C. to170° C., for from 1 to 5 hrs. The derivatized polymers of the presentinvention can also be treated with polymerizable lactones (such asepsilon-caprolactone) to form dispersant adducts.

Lubricating Compositions

The Koch functionalized polymer, in addition to acting as intermediatesfor dispersant and MFVI manufacture, can be used as molding releaseagents, molding agents, metal working lubricants, point thickeners andthe like. The primary utility for the products of the invention, fromfunctionalized polymer all the way through post-treated derivatizedpolymer, is as additives for oleaginous compositions.

The additives of the invention may be used by incorporation into anoleaginous material such as fuels and lubricating oils. Fuels includenormally liquid petroleum fuels such as middle distillates boiling from65° C. to 430° C., including kerosene, diesel fuels, home heating fueloil, jet fuels, etc. A concentration of the additives in the fuel is inthe range of typically from 0.001 to 0.5, and preferably 0.005 to 0.15wt. %, based on the total weight of the composition, will usually beemployed.

The additives of the present invention may be used in lubricating oilcompositions which employ a base oil in which the additives aredissolved or dispersed therein. Such base oils may be natural orsynthetic. Base oils suitable for use in preparing the lubricating oilcompositions of the present invention include those conventionallyemployed as crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, such as automobile andtruck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing the additivemixtures of the present invention in base oils conventionally employedin and/or adapted for use as power transmitting fluids, universaltractor fluids and hydraulic fluids, heavy duty hydraulic fluids, powersteering fluids and the like. Gear lubricants, industrial oils, pumpoils and other lubricating oil compositions can also benefit from theincorporation therein of the additives of the present invention.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halosubstitutedhydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,polybutylenes, polypropylenes, propylene-isobutylene copolymers,chlorinated polybutylenes, etc. Alkylene oxide polymers andinterpolymers and derivatives thereof where the terminal hydroxyl groupshave been modified by esterification, etherification, etc., constituteanother class of known synthetic lubricating oils. Another suitableclass of synthetic lubricating oils comprises the esters of dicarboxylicacids. Esters useful as synthetic oils also include those made from C₅to C₁₂ monocarboxylic acids and polyols and polyol ethers such asneopentyl glycol, etc. Silicon-based oils such as the polyalkyl-,polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oilscomprise another useful class of synthetic lubricants. Unrefined,refined and rerefined oils can be used in the lubricants of the presentinvention.

The additives of the present invention, particularly those adapted foruse as dispersants or viscosity modifiers, can be incorporated into alubricating oil in any convenient way. Thus, they can be added directlyto the oil by dispersing or dissolving the same in the oil. Suchblending into the additional lube oil can occur at room temperature orelevated temperatures. Alternatively the additives may be first formedinto concentrates, which are in turn blended into the oil. Suchdispersant concentrates will typically contain as active ingredient(A.I.), from 10 to 80 wt. %, typically 20 to 60 wt. %, and preferablyfrom 40 to 50 wt. %, additive, (based on the concentrate weight) in baseoil. MFVI concentrates typically will contain from 5 to 50 wt. % AI.

The additives of the invention may be mixed with other additivesselected to perform at least one desired function. Typical of suchadditional additives are detergents, viscosity modifiers, wearinhibitors, oxidation inhibitors, corrosion inhibitors, frictionmodifiers, foam inhibitors, rust inhibitors, demulsifiers, antioxidants,lube oil flow improvers, and seal swell control agents.

Compositions, when containing these additives, typically are blendedinto the base oil in amounts which are effective to provide their normalattendant function. Representative effective amounts of such additivesare illustrated as follows:

    ______________________________________                                                          (Broad)    (Preferred)                                      Compositions      Wt %       Wt %                                             ______________________________________                                        V.I. Improver        1-12       1-4                                           Corrosion Inhibitor                                                                              0.01-3     0.01-1.5                                        Oxidation Inhibitor                                                                              0.01-5     0.01-1.5                                        Dispersant         0.1-10     0.1-5                                           Lube Oil Flow Improver                                                                           0.01-2     0.01-1.5                                        Detergents and Rust                                                                              0.01-6     0.01-3                                          Inhibitors                                                                    Pour Point Depressant                                                                            0.01-1.5   0.01-1.5                                        Anti-Foaming Agents                                                                             0.001-0.1  0.001-0.01                                       Antiwear Agents   0.001-5    0.001-1.5                                        Seal Swellant      0.1-8      0.1-4                                           Friction Modifiers                                                                               0.01-3     0.01-1.5                                        Lubricating Base Oil                                                                            Balance    Balance                                          ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates or packages comprisingconcentrated solutions or dispersions of the subject additives of thisinvention together with one or more of said other additives. Dissolutionof the additive concentrate into the lubricating oil may be facilitatedby solvents and by mixing accompanied with mild heating, but this is notessential. The final formulations may employ typically 2 to 20 wt. %,e.g. about 10 wt. %, of the additive package with the remainder beingbase oil.

All of said weight percents expressed herein (unless otherwiseindicated) are based on active ingredient (A.I.) content of theindividual additives, and the total weight of the additive package orformulation, which will include the weight of total oil or diluent.

EXAMPLES

Composition parts and percents are by weight unless otherwise indicated.All molecular weights (Mn) are number average molecular weight.

Examples 1-13 Yield of Carboxylic Acid Group (Examples 1-5) Example 1(Comparative)

34.5 parts of poly-n-butene polymer (PNB) (Mn=550) dissolved in 36.2parts of n-heptane (nC₇) were charged to an autoclave, mixed and heatedto 50° C. 662 parts of BF₃ dihydrate (BF₃.2H₂) were then chargedfollowed immediately by CO which brought the total autoclave pressure to1,500 psig. The mixture was stirred for 3 hrs. at temperature andpressure. Pressure was released, and the reaction product was washedwith copious amounts of water and butanol to free the polymer phase fromthe acid phase. The polymer was dried in an oven. The analysis of thefinished polymer showed less than 5% conversion to the carboxylic acidgroup.

Example 2

The procedure described in Example 1 was then followed except, 37.1parts of PNB (Mn=550) was dissolved in 40.2 parts of nC₇, and 690 partsof BF₃.1.2H₂ O was substituted for the BF₃.2H₂ O and prepared bybubbling BF₃ gas into BF₃.2H₂ O until sufficient BF₃ was absorbed togive the desired composition. The pressure was brought to 2,000 psigwith CO. Analysis of the final product showed 85% conversion of thepolymer to neo-carboxylic acid.

Example 3

The procedure described in Example 1 was followed except that 203.6parts of ethylene propylene (EP) copolymer (Mn=1800, and about 50 wt. %ethylene) and 159.9 parts of nC₇, and 34 parts of BF₃. 1.1 H₂ weresubstituted for the charges of reactants. The pressure was brought to2,000 psi with CO. The conversion to neocarboxylic carboxylic acid was56%.

Example 4

The procedure described in Example 1 was followed except 803 parts ofethylene butene (EB) copolymer (Mn=3,700 about 45 wt. % ethylene), 568parts of iso-octane, and 670 parts of BF₃ 1.1 H₂ O were used. Thepressure was brought to 2,000 psig with CO. The reaction product wasdischarged into an aqueous solution containing 600 parts of sodiumfluoride (NaF), 756 parts of water, 302 parts of hexane, and 50 parts ofbutanol. The polymer product readily separated from the aqueous phase,was recovered, and dried. Analysis showed 85.1% conversion toneo-carboxylic acid.

Example 5

The procedure described in Example 4 was followed except 543 parts ofpropylene butylene (PB) copolymer (Mn=2,800, and about 30 wt. %propylene) 454 parts of iso-octane, and 659 parts of BF₃.1.1 H₂ O wereused. The reaction product was discharged into 600 parts sodiumfluoride, 945 parts water, and 302 parts hexane. The analysis of thefinal product showed 75.4% conversion to neo-carboxylic acid. Theresults of Examples 1-5 are summarized in Table 1 below:

                  TABLE 1                                                         ______________________________________                                                                    Catalyst Yield                                    Example   Polymer  Mn       Complex  (%)                                      ______________________________________                                        Comp.                                                                         1         PNB       550     BF.sub.3.2H.sub.2 O                                                                    5                                        2         PNB       550     BF.sub.3.1.2H.sub.2 O                                                                  85                                       3         EP       1800     BF.sub.3.1.1H.sub.2 O                                                                  56                                       4         EB       3700     BF.sub.3.1.1H.sub.2 O                                                                  85.1                                     5         PB       2800     BF.sub.3.1.1H.sub.2 O                                                                  75.4                                     ______________________________________                                    

Alkyl Ester (Examples 6-12) Example 6 (Comparative)

The procedure described in Example 1 was followed except, 1119.2 partsof PNB (Mn=550) without solvent, and 350 parts of BF₃. dibutanol(prepared by bubbling BF₃ gas into n-butanol) were used. The pressurewas brought to 2000 psig with CO. The analysis of the final productshowed less than 5% conversion to neo-alkyl ester.

Example 7

The procedure described in Example 1 was followed except, 153.3 parts ofEP polymer (Mn=900, about 50 wt. % ethylene) and 137.9 parts nC₇, and 88parts of BF₃. monobutanol was used in the recipe. The polymer was dried,and the conversion to neo-alkyl ester was 86%.

Example 8

The procedure as described in Example 4 was followed except 143 parts ofPNB (Mn=550), without solvent, and 37 parts of BF₃. monomethanol(prepared by bubbling BF₃ gas into methanol) (BF₃.CH₃ OH) was used. Thereaction product was discharged into 230 parts of ammonium fluoride and765 parts methanol. The conversion was 91.3% to the neo-methyl ester.

Aryl Ester Example 9

The procedure described in Example 1 was followed except 440 parts ofPNB (Mn=550), without solvent, and 244 parts of BF₃. tetra(4-chlorophenol) was used. The BF₃ complex was prepared by bubbling BF₃gas into melted 4-chlorophenol. The autoclave was pressured to 1,485psig with CO, and the reaction was held at 35 55° C. for 2 hrs. Analysisshowed the following results:

    ______________________________________                                        Yield to 4 chloro phenyl neo-ester/acid                                                            = 60% of polymer                                         to alkyl phenyl ester                                                                              = 11.7% of polymer                                       to alkyl phenol      = 10.1% of polymer                                       Total Yield          = 81.8% polymer                                                                 converted                                              ______________________________________                                    

Example 10

(catalyst complex)

A complex of BF₃ with 4-chlorophenol was prepared by bubbling BF₃ intomelted 4-chlorophenol. In order to enhance the uptake of BF₃ gas togenerate BF₃.di(4-chlorophenol) the solution was cooled. After severalminutes, the solution solidified. Melting the complex resulted in rapidliberation of BF₃.

(Carbonylation)

An autoclave was charged with 391 psig of BF₃ gas at 30° C., followed byan additional 118 psig of CO, to a total pressure of about 500 psig.While stirring the autoclave, a mixture of 440 parts PNB (Mn=550) and108 parts of 3-fluoro-phenol was charged to the reactor, and thepressure was brought to 1500 psig with CO, and the temperature to 50° C.The reaction was held at these conditions for 2 hrs. and the autoclavewas then depressurized. The reaction product was stripped to remove BF₃gas and excess substituted phenol. The final product analysis showed91.5% yield. Example 11

The procedure of Example 10 was followed, except the autoclave waspressured to 199 psig with BF₃ at 50° C., followed by 301 psig of CO, tobring the total pressure to 500 psig and 406 parts of EB copolymer(Mn=4600, 20 wt. % ethylene) and 100.6 parts of 2,4-dichlorophenol(pKa=7.85) at 50° C. were charged to the autoclave and pressured to 1430psig with CO. The yield was 84.5%.

Example 12

The procedure in Example 10 was followed except the autoclave waspressured to 254 psig with BF₃ at 50° C., followed by 254 psig of CO tobring the total pressure to 508 psig; and, 110 parts EB polymer(Mn=2,200, about 50% ethylene) 31 parts of dichlorophenol (pKa =7.85) at50° C. were charged to the autoclave, and pressurized to 2,000 psig withCO. The conversion was 85.4%. The results of Examples 6-9 and 10-12 aresummarized in Table 2 below:

                  TABLE 2                                                         ______________________________________                                                                Catalyst       Yield                                  Example                                                                              Polymer  Mn      Complex        (%)                                    ______________________________________                                        Comp.                                                                          6     PNB      550     BF.sub.3.dibutanol                                                                           5                                       7     EB       900     BF.sub.3.monobutanol                                                                         86                                      8     PNB      550     BF.sub.3.monomethanol                                                                        91.3                                    9     PNB      550     BF.sub.3.tetra(4-chlorophenol)                                                               81.8                                   10     PNB      550     *BF.sub.3 +-fluorophenol                                                                     91.5                                   11     EB       4600    *BF.sub.3 2,4-dichlorophenol                                                                 84.5                                   12     EB       2200    *BF.sub.3 +dichlorophenol                                                                    85.4                                   ______________________________________                                         *Catalyst and phenolic compound added separately in one step.            

Examples 13-17 Amination Reaction of PNB-neo carboxylic acid with PAMExample 13

200 parts the PNB neocarboxylic acid prepared by a process similar tothat of Example 2 and 31.2 parts of poly(ethyleneamine) averaging 5-8nitrogens per molecule (PAM) were charged into a reactor with stirring.The reactor contents were purged with nitrogen. The reactor was sealedand the pressure was brought to 60 psig with nitrogen. The reactor washeated to 240° C. for five hrs. The contents were then sparged withnitrogen via a dip tube and overhead vent line and cooled at 30° C. Theyield of carboxylic acid amide by ¹³ C-NMR was 45.4%.

Example 14

374 parts of neo acid functionalized EB copolymer of Example 4 dissolvedin 700 parts heptane were charged to a reactor vessel. The solution washeated with mixing to 90° C. Then, 70 parts of thionyl chloride wasslowly added to the solution, plus an additional 300 parts of heptane.After the reaction to the acid chloride was complete, the solution washeated to 100° C. at atmospheric pressure with N₂ sparging followed byhigh vacuum flashing to remove reaction by-products and heptane. Theacid chloride product was cooled. Then, fresh, dry heptane was added tothe acid chloride product. The acid chloride product was then heated to90° C. Then, 10 parts of polyamine (PAM) and 17.8 parts of triethylaminewere slowly added to the acid chloride. The reaction mixture wasfiltered and excess triethylamine was stripped to produce the aminatedproduct as shown by infrared analysis.

Example 15

17.8 parts of the 2,4-dichlorophenyl ester of the EB copolymer ofExample 11 were charged to a reaction vessel. The vessel contents wereheated to 80° C. with mixing. Then 0.442 parts of polyamine (PAM) wascharged to the vessel. The vessel contents were than slowly heated overa period of 8 hrs. from 150° C. to 220° C. while refluxing the liberateddichlorophenol (pKa=7.85). After complete conversion to the amide, thephenol was removed by N₂ sparging. The vessel contents were cooled toambient temperature. C¹³ NMR analysis showed quantitative conversion ofester to amide.

Example 16

The procedure as described in Example 15 was followed, except 20.2 partsof the 2,4-dichlorophenyl ester of Example 12 was used with 0.954 partsof PAM. C¹³ NMR analysis showed quantitative conversion of ester toamide.

Example 17

19.4 parts of the aminated polymer described in Example 16 was mixedwith 10.0 parts of base oil and heated to 140° C. in a reaction vesselwith mixing. Then 1.407 parts of milled 30% boric acid slurry in baseoil was slowly added to the vessel contents. The reactor was spargedwith N₂ at temperature for two hrs., then an additional 6.26 parts ofbase oil was added to the reaction vessel. The vessel contents werecooled to 120° C., and filtered. Analysis of the product showed a 45%active ingredient level (0.73% N, 0.26% B).

Example 18

An ethylene/butene copolymer (46% ethylene, Mn=3,300) prepared viaZiegler-Natta polymerization with zirconium metallocene catalyst andmethyl alumoxane cocatalyst according to known procedures wascarbonylated with carbon monoxide in the presence of BF₃ and2,4-dichlorophenol in a continuous stirred tank reactor at 50° C. Thepolymer conversion was 85%.

Example 19

The ester of example 18 was aminated with a polypropylene tetraaminewith one end substituted with a tallow group with approximately oneprimary amine per molecule and a nitrogen content of 12.4% using 1.2 eq.of primary amine per carbonyl. The reagents were mixed at roomtemperature and heated to 200° C. for 7 hrs. while nitrogen stripping toremove the phenol by distillation. The reaction mixture analyzed for 99%conversion to the corresponding amide. About 150 g of the above amidewas diluted in 99 g of S150N mineral oil and heated to 145° C. (9.35 gof a 30% boric acid slurry in oil was added over one hour). Afteraddition was complete, the temperature was raised to 150° C. and thereaction mixture was nitrogen stripped for one hour. The 50% solutionanalyzed for 0.46% N and 0.18% B. The viscosity at 100° C. is 646 cSt.

Example 20

The ester of example 18 was heated to 180° C. and mixed with thetetraamine of example 19 using 1.1 eq. of primary amine per carbonyl.Vacuum was applied and the reaction mixture was heated at 180° C. undervacuum of 10-20 mm Hg for 8 hrs. while removing the phenol bydistillation. The infrared analysis showed incomplete conversion toamide. Vacuum was applied at 200° C. for another 4 hrs. to obtain 99.2%conversion. The amidated product analyzed for 0.90% nitrogen. About1,530 g of the above amide were diluted with 1,207 g of SI50N and heatedto 145° C. About 122 g of a 30% boric acid slurry was added in one hour.The temperature was raised to 150° C. and nitrogen stripped for onehour. The filtered 50% solution analyzed for 0.54% N and 0.15% B. Theviscosity at 100° C. is 416 cSt.

Example 21

An ethylene/butene copolymer (35% ethylene, Mn=3,900) prepared viaZiegler-Natta polymerization with zirconium metallocene catalyst andmethyl alumoxane cocatalyst according to known procedures wascarbonylated with carbon monoxide in the presence of BF₃ and2,4-dichlorophenol in a continuous stirred tank reactor at 50° C. Thepolymer conversion was 85%.

The ester was aminated with the tetramine of example 20 using the vacuumprocess at 200° C. About 1,700 grams of the ester were heated to 200° C.and 159.8 g of the tallow tetraamine was added. Vacuum (2-4 mm Hg) wasapplied at 200° C. until the infrared analysis showed 99% conversion.The amide analyzed for 0.88% nitrogen. About 1,685 g of this amide wasdiluted with 1,377 g of S150N and heated to 145° C. Then 118 g of a 30%boric acid-oil slurry was added over one hour. The resulting product wasnitrogen stripped at 150° C. for one hour and filtered. The filtered oilsolution analyzed for 0.43% N, 0.1% B and a kinematic viscosity at 100°C. of 264 cSt.

Example 22

The ester of example 18 was aminated with a polypropylene etherpentamine with only one end substituted with a dodecyl alkyl group withapproximately one primary amine group per molecule and a nitrogencontent of 12.92% using 1.1 eq. of primary amine per carbonyl. Thereagents were mixed at room temperature and heated to 220° C. for 4 hrs.The product was then stripped with nitrogen for 3 hrs. at 220° C. Theamide analyzed for 0.83% N. About 1,540 g of the amide were diluted with810 g of S150N. The oil solution was then borated at 145° C. with 105 gof a 30% boric acid slurry as previously described. The filtered productanalyzed for 0.44% nitrogen and 0.23% B with a kinematic viscosity at100° C. of 1,288 cSt.

Example 23

An ethylene/butene copolymer ester (54% ethylene Mn =3,600) was preparedas in example 18 (85% yield). The ester was aminated with2-ethylhexylaminopropylaminopropylaminopropylamine with approximatelyone primary amino group per molecule and a nitrogen content of 18.24%using 1.1 equivalent of primary amine per carbonyl. The ester was heatedto 200° C. and the amine was added. The reaction mixture was vacuumheated (10-20 mm Hg) for several hours until the reaction showedcomplete conversion to the amide. The amide was nitrogen stripped andanalyzed for 0.96% N. The product was diluted in mineral oil to make a50% solution and borated using our standard technique. The filteredproduct analyzed for 0.55% N, 0.23% B and a kinematic viscosity of 977cSt at 100° C.

Example 24

235 g of the EB ester of example 18 was heated to 180° C. and 23 g ofdimethylaminopropylaminopropylamine (DMAPAPA) having approximately oneprimary amine group per molecule and a nitrogen content of 25.44% wasadded. The reaction mixture was heated at 180° C. for several hours andchecked by IR. At the end of 4 hrs. at 180° C., it appeared to be 99+converted to the corresponding amide. The product was nitrogen strippedat 180° C. for 4 hrs. to distill off the unreacted amine. The strippedproduct analyzed for 0.86% N (0.83% theory).

Example 25

235 g of the EB ester of example 18 was heated to 180° C. and 32 g ofdimethylaminopropylaminopropylaminopropylamine (DMAPAPAPA) havingapproximately one primary amine group per molecule and a nitrogencontent of 25.4% was added. The reaction was heated to 180° C. undernitrogen atmosphere for several hours until the IR showed 99+conversion. After 4 hrs. at 180° C. it showed complete conversion to theamide. The product was then stripped at 220° C. for 3 hrs. to remove theunreacted amine. It analyzed for 1.02% N.

Example 26

An ethylene butene copolymer (40% ethylene, Mn =2,500) prepared viaZiegler-Natta polymerization as in example 18 was carbonylated in thepresence of hexafluoroisopropanol with the process of example 2 (80%yield).

About 150 grams of the above ester was aminated with 39.7 g of the onearmed amine dimethylaminopropylaminepropylamine (DMAPAPA) at 200° C.under a nitrogen blanket until the IR showed better than 99% conversion.The reaction mixture was nitrogen stripped at 200° C. for 2 hrs. todistill off the unreacted amine. The product is calculated to have,theoretically, 0.80% N.

Example 27 (Comparative example)

The polymer ester of example 18 was aminated with an ethylenepolyaminecontaining between 2 and 3 primary amine groups per molecule and anitrogen content of 32.8%. About 1,776 g of the ester was heated to 200°C. and 64.7 g of the polyamine added. Vacuum was applied (2-10 mm Hg)and the reaction was heated at 200° C. under vacuum until 99% conversionto the amide as indicated by IR analysis. The stripped 40% solutionanalyzed for 1.14% nitrogen. About 1,657 g of the amide was mixed with1,592 grams of diluent oil and borated with 120.5 g of a 30% Boric acidoil slurry. The borated product analyzed for 0.54% N, 0.184% B and akinematic viscosity of 3,771 cSt at 100° C. Compare this to theviscosity of the borated ester of Example 20 of the invention (416 cSt)which also has 0.54 % N and similar boration but made with thepolypropylene tetra amine of the invention.

We claim:
 1. A dispersant comprising a functionalized hydrocarbonpolymer derivatized by reaction with a polyamine having one primaryamino group and 1 to 10 secondary or tertiary amino groups, wherein thehydrocarbon polymer is other than gem-structured polyolefin and has anumber average molecular weight of at least 500 and the functionalizedhydrocarbon polymer is functionalized by direct attachment of groups ofthe formula --CO--Y--R³, wherein Y is O or S and R³ is either (i) H orhydrocarbyl and at least about 50 mole percent of the functional groups--CO--Y--R³ are attached to a tertiary carbon atom of the polymerbackbone or (ii) aryl, substituted aryl, or substituted hydrocarbyl. 2.The dispersant according to claim 1, wherein R³ is aryl, substitutedaryl or substituted hydrocarbyl and at least 60 mole percent of thefunctional groups --CO--Y--R³ are attached to a tertiary carbon atom ofthe polymer backbone.
 3. The dispersant according to claim 1, whereinthe hydrocarbon polymer comprises a member selected from the groupconsisting of polyalkene homopolymers, polyalkene interpolymers, andmixtures thereof.
 4. The dispersant according to claim 1, wherein thehydrocarbon polymer comprises a member selected from the groupconsisting of alpha-olefin homopolymers, alpha-olefin interpolymers andethylene alpha-olefin copolymers.
 5. The dispersant according to claim4, wherein the hydrocarbon polymer comprises ethylene alpha-olefincopolymer derived from ethylene and at least one alpha-olefin having theformula H₂ C=CHR⁴ wherein R⁴ is straight chain or branched chain alkylradical comprising 1 to 18 carbon atoms and wherein at least about 30%of the polymer chains possess terminal vinylidene unsaturation.
 6. Thedispersant according to claim 5, wherein the ethylene alpha-olefincopolymer has a number average molecular weight of from 500 to 10,000.7. The dispersant according to claim 5, wherein the ethylenealpha-olefin copolymer comprises ethylene-butene-1 copolymer.
 8. Thedispersant according to claim 1 wherein the hydrocarbon polymer has anumber average molecular weight of from 500 to 20,000.
 9. The dispersantaccording to claim 1, wherein the primary amino group and the 1 to 10secondary or tertiary amino groups of the polyamine are separated by ahydrocarbylene group.
 10. The dispersant according to claim 9, whereinthe hydrocarbylene group comprises a propylene (--CH₂ --CH₂ --CH₂ --)group.
 11. The dispersant according to claim 1, wherein the polyaminecomprises volatile polyamine.
 12. The dispersant according to claim 1,wherein the polyamine comprises a polyamine of the formula: H₂ N(--R⁵--NH)_(z) --(R⁶ --A)_(y) --R₇ wherein R⁵ and R⁶ are hydrocarbyl groupsof 1 to 6 carbons; R⁷ is a hydrocarbyl group of 1 to 40 carbons or aheterocyclic structure containing at least one of N or S; A is 0 or S; zis 1 to 10; and y is 0 or
 1. 13. The dispersant according to claim 1,wherein the dispersant is post-treated with a boron compound to obtain aborated dispersant.
 14. A lubricating oil composition comprising a baseoil and the dispersant according to claim
 1. 15. The dispersantaccording to claim 1, wherein R³ is H or hydrocarbyl, and --Y--R³ has apKa<12.
 16. An oleaginous composition in the form of a lubricating oilor lubricating oil additive package comprising the dispersant of claim15 and a base oil.
 17. The dispersant according to claim 15 wherein theprimary amino group and the 1-10 secondary or tertiary amino groups ofthe polyamine are separated by a propylene (--CH₂ --CH₂ --CH₂ --)group.18. The dispersant according to claim 15 wherein said polyaminecomprises volatile polyamine.
 19. The dispersant according to claim 15wherein said polyamine comprises a polyamine of the formula: H₂ N(R₅--NH)_(z) --(--R₆ --A)_(y) --R⁷ wherein R⁵ and R⁶ are hydrocarbyl groupsof 1 to 6 carbons; R⁷ is a hydrocarbyl group of 1-40 carbons or aheterocyclic structure containing at least one of N or S; A is O or S;z=1-10; and y=0or
 1. 20. The dispersant according to claim 15 whereinsaid polyamine comprises a polyamine prepared by stepwise reacting analcohol, a monoamine or a polyamine with acrylonitrile and thenhydrogenating the product thereof.
 21. A fuel composition comprising adispersant of claim 15.